Photographic light-sensitive material

ABSTRACT

Photographic light-sensitive material especially for the silver dyestuff bleaching process is provided. This material contains on a support at least one layer having at least one cyan dyestuff of the formula   IN WHICH A is a hydroxynaphthalene radical which may be substituted by an amino or hydroxyl group and which contains at least one sulfonic acid or sulfonic acid amide group, the hydroxyl group being in the ortho position to the azo group, D is hydrogen, halogen, alkyl, alkoxy, hydroxyalkoxy or acylamino and R is an organic radical bound to the benzene radical through an NH- or -N N- bridge, m is at most 3 and the dyestuff contains at least two sulfonic acid groups per molecule. These dyestuffs are diffusion resistant and form stable aqueous solutions, are insensitive to calcium ions and can be bleached white.

United States Patent Inventors Hansrolf Loeffel Bern; John Lenoir; Bernhard Piller, both of Marly-le-Petit, all of Switzerland [2|] Appl. No. 28,544 [22] Filed Apr. 14, 1970 [45] Patented Jan. 11, 1972 [73] Assignee Ciba Limited Basel, Switzerland [32] Priority Apr. 18, 1969 [3 3 Switzerland [31 5897/69 [54] PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL 16 Claims, No Drawings [52] U.S. Cl 96/99, 96/73, 96/53, 96/20 [51] Int. Cl G03c 1/10, G03c 1/76 [50] Field of Search 96/99, 73, 53, 20

[5 6] References Cited UNITED STATES PATENTS 3,119,811 1/l964 Dreyfuss 96/99 Primary ExaminerNorman G. Torchin Assistant Examiner- Edward C. Kimlin Attorneys- Harry Goldsmith, Joseph G. Kolodny and Mario A. Monaco Dreyfuss ABSTRACT: Photographic light-sensitive material especially for the silver dyestuff bleaching process is provided. This material contains on a support at least one layer having at least one cyan dyestuff of the formula I in which A is a hydroxynaphthalene radical which may be substable aqueous solutions, are insensitive to calcium ions and can be bleached white.

PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL This invention provides photographic light-sensitive material especially for the silver dye bleaching process that contains on a support at least one layer having at least one dyestuff of 5 lheformula J J W oo 7 g r V r a (1) NH, NH-C 00-, o 0-0-, -o-o 0- A-N=N R Q 10 S O;-N/-S O;NH, -N/ or NHS 0 It is advantageous to use dyestuffs of the formula (3) Al E [N=N-K] n 1 H 0,8 ](l ](2 moist-1 LN D u (n1)+rn(2n) H wherein A denotes a hydroxynaphthalene radical which may wherein A denotes a hydrogen atom or an amino or hydroxyl be substituted by an amino or hydroxyl group which may be group which may be further substituted,p=l or 2, and E, D, G, fuiger s ubstituted, and which contains at least one sulphonic jgm and n have the significance indicated, the hydroxyl group acid or sulphonic acid amide P- y y g p g being in the lor 2-position and A being in the 8-position of in the ortho-position to the azo group, D denotes a hydroge the naphthalene radical, the azo group being in the ortho-posihalogen atom, a lower alkyl, lower alkoxy lower y tion to the hydroxyl group, and the dyestuff containing at least yalkoxy group or an acylamino group, E denotes a lower alkyl, two l h i id groups er molecule. hydroxyalkyl or carboxyalkyl group, R denotes an organic radical which is bound to the benzene radical through an Good results are particularly obtained with dyestuffs of the NH- or N N- bridge, and m denotes an integer having a formula value of at most 3, the dyestutf containing at least two hhq isssiqs euesu molecule- Preference is given to photographic material which contains wherein A denotes an amino group which may be substituted at least one dyestuff of the formula V by lower alkyl, aryl, cycloalkyl or acyl groups or a hydroxyl 2 group which may be substituted by a lower alkyl, hydroxyalkyl (H) or aralkyl group, and E, D, G, K, m, n and 2 have the sign nificance indicated, the dyestuff containing at least two sulphonic acid groups per molecule. The lower alkyl groups A-N= preferably contain at most five carbon atoms.

D M I V (n 1)+-m(2 q2 V at Of special interest are dyestuffs of the formula wherein K denotes an aromatic or heterocyclic radical having wherein A denotes a radical of the formula at most 3 ring members, G denotes an acyl radical bound to m X NH groups through m acyl groups, and n=1 or 2, and A, or D, E and m have the significance indicated, the dyestuf'f containing at least two sulphonic acid groups per molecule. 7 5 .l i-

in which X, represents a hydrogen atom, or a methyl or ethyl The radical K in the formula (2) can be substituted in the group, X represents a h d g n atom or a methyl, ethyl or diverse Ways, for example y halogen atoms, hydroxyli cyclohexyl group, a phenyl group which may be further subammo, carboxylic acid, carboxylic acid amide, sulphonic acid, u r d or an l group, the acyl group being derived from an sulphonic acid amide, urea or nitro groups. Further radicals organic mono or l a b xyli or -sulphonic acid or from for example alkyl, cycloalkyl, aralkyl or aryl radicals or N heterocyclic m ound containing hydroxyl groups, X heterocyclic radicals may also be bound to the radical K 'Ep' a hydrog n atorn or a methyl, ghyhhydroiiyethyl m y or through bridge membersor benzyl group, and E, D, G, K, m, n and p have the significance indicated, the dyestuff containing at least two Suitable bridge members are for example those of s lphonic acid groups per molecule. the formulae Here dyestuffs of the formula Erna are particularly advantageous, wherein A denotes a radical of thc formula.

N or OX in which X and X have the monocarboxylic or dicarboxylic acid having at most 10 carbon atoms, or from an aromatic monoor di-carboxylic or sulphonic acid, or from a heterocyclic monocarboxylic or dicarboxylic acid or from an N-heterocyclic compound conare preferred, wherein A.,, D, E, G, K, m, n and p have the significance indicated, the dyestuff containing at least two sulphonic acid groups per molecule.

Photographic material which contains at least one dyestuffof the formula wherein D denotes a hydrogen or chlorine atom or a methyl, methoxy, ethoxy, hydroxyethoxy or acetylamino group, and

taining hydroxyl groups and possessing acidic characteristics; 30 A, E, G, K, m and n have the significance indicated, the

E, D, G, K, m, n and p have the significance indicated, the dyestuff containing at least two sulphonic acid groups per molecule.

can be derived are as a rule preferably naphthalene or 4 benzene carboxylic or sulphonic acids, which can in turn be dyestuff containing at least two sulphonic acid groups per molecule, is preferred.

Here dyestuffs of the formula are of particular interest, wherein D denotes a hydrogen atoin substituted yet further by alkyl, perfluoralkyl, alkoxy, amino, SS wherein E, represents a methyl, ethyl or hydroxyethyl radical acylamino, carboxyl, carboxylic acid amide, sulphonic acid, sulphonic acid amide, alkylsulphone, nitro, alkylcarbonyl or arylcarbonyl groups or halogen atoms. The alkyl radicals occurring in these substituents are preferably lower alkyl radicals having at most five carbon atoms. Acyl'radicals which are 60 derived from an N-heterocyclic compound containing hydroxyl groups and possessing acidic characteristics are primarily pyrimidyl radicals and above all 1,3,5-triazinyl radicals, which are preferably further substituted. Acyl radicals of heterocyclic carboxylic acids are for example derived from pyridine, 65

furane or thiophene carboxylic acids.

Among the dyestuffs of formula (6), those ofthejormula and the radicals D and E,-S- are in the paraposition to one another, A, D G, K, m and n have the significance indicated, and the dyestuff molecule contains at least two sulphonic acid groups.

Where n=2, in formula (2), the dyestuffs preferably correspond to the formula least one dyestutf of the formula wherein K, denotes a benzene, naphthalene pyrazolone radical which may be substituted, and A, E and D have the significance indicated, the dyestuff molecule containing at least two sulphonic acid groups.

Dyestuffs of the formula sulphonic idgroup or apyrazolone @dicalofthe formula fwiierein T represents a benzene or naphthalene radical which may be substituted by alkyl, alkoxy, phenoxy, carboxylic acid,

carboxylic acid amide, sulphonic acid, or sulphonic acid amide groups, amino or acylamino groups which may be further substituted, or halogen atoms, 0 represents an alkyl, carboxylic acid, carboxylic acid alkyl ester, benzene, amino or acylamino radical, and A, D and B have the significance in-. dicated, the dyestufi molecule containing at least two 9 sulphonic acid groups.

Where the radical K represents an acylaminobenzene radical, the acyl radical is derived from an aliphatic, heterocyclic or aromatic monocarboxylic or dicarboxylic acid. Thus K may contain a simple acyl group, for example an acetyl radical, or an acyl group which still contains a free acid radical, for example a radical of the formula OCCH=CHCOOH. Furthermore, two radicals K may be bound to one another by two amide functions through the diacyl radical. Monoacyl radicals are preferably derived from aliphatic carboxylic acids, for example acetic acid or propionic acid, or from benzene carboxylic acids which may be substituted. Suitable diacyl radicals are, for example, CO, glutaryl, fumaryl, terephthaloyl, isophthaloyl, thiophene-2,5 dicarbonyl, furane- 2,5-dicarbonyl or pyridine-2,6-dicarbonyl radicals or also. radicals of the formula Photographic material is also preferred which contains at the substituent K, are preferably derived from aromatic amines, especially from anilines which may be further substituted. The amine radicals in the sulphonic acid amide radicals of the substituent K are preferably derived from lower monoalkylamines or dialkylamines, lower hydroxyalkylamines, anilines which may be substituted, N-alkylanilines or secondary heterocyclic amines. The lower alkyl radicals preferably contain at most five carbon atoms.

Very suitable dyestuffs of formula (13) correspond to the i rmi i wherein 2,, Z and 2,, each represents a hydrogen atom or a sulphonic acid or sulphonic acid amide group, Y, represents a hydrogen atom or a hydroxyl, alkoxy, hydroxyalkoxy, aralkoxy or alkylamino group, the alkyl radical in each case containing at most five carbon atoms, or an amino, cyclohexylamino, phenylamino or acylamino group, the acyl radical having the above mentioned significance, Y represents a hydrogen atom or a carboxylic acid or carboxylic acid amide group and A, D and E have the significance indicated, each dyestuff molecule containing at least two sulphonic acid groups and the righthand side azo group in formula (14) being in the 2-, 5- or 8- position of the l-naphthol radical.

When rz=l in formula (2), the dyestuffs preferably correspond to the formula 1) wherein G, denotes an acyl radical, bound thrcmgh m acyl groups to m -NH- groups, of a substituted or unsubstituted aliphatic monocarboxylic or dicarboxylic acid or monosulphonic acid, a substituted or unsubstituted aromatic monoor di-carboxylic or -sulphonic acid, a heterocyclic monocarboxylic or dicarboxylic acid or a substituted or unsubstituted Nheterocyclic compound containing hydroxyl groups and possessing acid characteristics, and A, D, E and m have the significance indicated, the dyestuff molecule containing at least two sulphonic acid groups.

The aromatic acyl radicals of the substituents G, are preferably derived from benzene monocarboxylic or dicarboxylic acids. The aliphatic acyl radicals radicals preferably contain at most 12 carbon atoms.

The acyl radicals of the N-heterocyclic compounds containing hydroxyl groups and possessing acid characteristics are preferably derived from heterocyclic compounds which possess six ring members and contain up to three ring nitrogen atoms; for example pyrimidine and particularly l,3,5'triazine radicals, which can be further substituted. These acyl radicals can all also contain free acid groups as substituents.

Dyestuffs of the formula are particularly suitable, wherein G denotes an acyl radical, bound through m acyl groups to m, -NH groups, of a substituted or unsubstituted aliphatic or aromatic monocarboxylic or di-carboxylic acid or of a heterocyclic monocarboxylic or di-carboxylic acid, m =l or 2, and A, D and E have the significance indicated, the dyestuff molecule containing at least two sulphonic acid groups.

Amongst these dyestuffs, those of the formula If s aliphatic dicarbo xylic acid having at most eight carbon atoms including carbonic acid, a substituted or unsubstituted benzene, thiophene, furane or pyridine dicarboxylic acid or an aromatic dicarboxylic acid of the formula l 7a) HOOCPhM-Ph-COOH wherein Ph and Ph each represents a substituted or unsubstituted phenylene radical and M represents an oxygen or sulphur atom or an SO CH CO or -HN CO-NH- group, m,=l or 2, and A, D and B have the significance indicated, the dyestutl' molecule containing at least two sulphonic acid groups.

Where m,=l, G is an acyl radical of an aliphatic carboxylic acid having preferably at most l0 carbon atoms, or a benzoyl radical which may be substituted further. Where m,=2, G is an aliphatic dicarboxylic acid radical, for example a --CO, glutaryl or fumaryl radical or an aromatic dicarboxylic acid radical, for example a terephthaloyl or isophthaloyl radical, or t a heterocyclic dicarboxylic acid radical, for example a thiophene, furane or pyridine dicarboxylic acid radical.

Particularly advantageous dyestuffs here correspond to the mu a III 8 wherein 6, denotes an acyl radical bound through m, acyl groups to m, NH- groups, and where m ,=l, a monoacyl radical of an aliphatic monocarboxylic acid having at most five carbon atoms or of a substituted or unsubstituted benzene 5 monocarboxylic acid and, where m,=2, a diacyl radical of glutaric, fumaric, terephthalic, isophthalic, thiophene-2,5-dicarboxylic or pyridinc-2,6-dicarboxylic acid or a radical of the formula CO or OCp-C,;H.,NHCO-NHp- C H CO, and A, D and E have the significance indicated, the dyestuff molecule containing at least two sulphonic acid I radicals.

Photographic material which contains at least one dycstuff of the following three fonnulas behaves particularly adi vantageously: (19) E in these for mm; A. Y V232,, ZQZQCL, p ahd m, i 5 have the significance indicated, and in formula 19) the right- Preferred dyestuffs of formulas (19) to (2l) are the I dyestuffs of the following formulas:

()CHa SOaII 11 sulphonic acid methoxypropylamide, 2-naphthol-6-sulphonic acid' methoxypropylamide, 2-naphthol-7-sulphonic acid methoxypropylamide, 2-naphthol-7-sulphonic acid phenylamide, 2-naphthol-7-sulphonic acid cyclohexylamide, 2- naphthol-7-sulphonic acid methylamide, 2-naphthol-7- sulphonic acid dimethylamide, 2-naphthol-7-sulphonic acid iso-propylamide, 2-naphthol-7-sulphonic acid morpholidamide, 2-naphthol-7-sulphonic acid ethylamide, 2-naphthol-7- sulphonic acid amide, 2-naphthol-7-sulphonic acid oxethylamide, 2-naphthol-7-benzylsulphone, 2-naphthol-7-sulphonic acid (4'-sulphophenyl)-amide, 2-naphthol-7-sulphonic acid N-methylpiperazide, 2-naphthol-7-sulphonic acid benzylamide, l-naphthol-B-sulphonic acid di-n-butylamide, lnaphthol-B-sulphonic acid di-n-propylamide, l-naphthol-3- sulphonic acid n-octylamide, l-naphthol-3-sulphonic acid amide, l-naphthol-3 -sulphonic acid methylamide, lnaphthol-S-sulphonic acid B-hydroxyethylamide, l-naphthol- 3-sulphonic acid phenylamide, 2-hydroxy-3-naphthoic acid (3'-carboxy)-anilide, 2-hydroxy-3-naphthoic acid (3',5'- dicarboxy)-anilide, 2-hydroxy-3-naphthoic acid (4-carb0xy) l-naphthylamide, 2-hydroxy-3-naphthoic acid (3-sulpho)- anilide, 2-hydroxy-3-napthoic acid (4-methoxy-3-sulpho)- anilide, 2-hydroxy-3-naphthoic acid (4'-chloro-3-sulpho)- anilide, 2-hydroxy-3-naphthoic acid (2'-methyl-3-chloro-5'- .sulpho)-anilide, 2-hydroxy-3-naphthoic acid (2-methoxy-4- nitro-3'-sulpho)-anilide, 2-hydroxy-3-naphthoic acid-(4'- phenoxy-2'-sulpho)-anilide, 2-hydroxy-3-naphthoic acid (4'- thiophenoxy-2-sulpho)-anilide, 2-hydroxy-3-naphthoic acid (3',42-hydroxy-3-naphthoic acid (4'- sulpho)-l'-naphthylamide, 2-hydroxy-3-naphthoic acid (3'- sulpho-4 '-[naphthyl-2 ]-thioether)-anilide, l-phenyl-3 -carboxy-pyrazolone-5, l-phenyl-3-B-ethoxy-carbethoxypyrazolone-S, l-phenyl-3-methyl pyrazolone-5 l-( 3 Poctanoylamino)-phenyl-3-carboxy-pyrazolone-5 l-( 3 '-sulpho- 4'-phenoxy)-phenyl-3-heptadecyl-pyrazolone-5 and l-(2- chloro-S '-sulpho )-phenyl-3-methyl-pyrazolone-5.

K can also represent radicals of such aminonaphthols as have been described for A.

Where m in fonnula (2)=l G is derived from anhydrides or especially from chlorides of monocarboxylic or monosulphonic acids, for example: acetic anhydride, propionyl chloride, methylsulphonic acid chloride, butyryl chloride, caproyl chloride, lauroyl chloride, stearoyl chloride, benzoyl chloride, toluene sulphonic acid chloride, 3,5-dinitrobenzoyl chloride, p-acetylaminobenzoyl chloride, nicotinic acid chloride, 3,4-dichlorobenzoyl chloride, thiophene-Z-carboxylic acid chloride and 4-chloro-3-nitrobenzoyl chloride.

Where m is 2 or 3, G is derived from anhydrides and especially from halides of acylating components which are at least dibasic.

As anhydrides succinic anhydride, chlorosuccinic anhydride or glutaric anhydride, may for example be mentioned.

Preferably however, the bridge members are derived from dihalides, and in particular, for example from phosgene, succinic acid dichloride, adipic acid dichloride, thiophosgene, glutaric acid dichloride, pimelic acid dichloride, chlorosuccinic acid dichloride, 2,3-dichlorosuccinic acid dichloride, fumaric acid dichloride, terephthaloyl chloride, isophthaloyl chloride, S-nitroisophthaloyl chloride, thiophene-2,5-dicarboxylic acid dichloride, furane-2,5-dicarboxylic acid dichloride, pyridine-2,5-dicarboxylic acid dichloride, pyridine-2,6-dicarboxylic acid dichloride, pyridine-3,5-dicarboxylic acid dichloride, pyrrole-2,5-dicarboxylic dichloride, diphenyl-urea-4,4dicarboxylic acid dichloride, diphenylketone-4,4-dicarboxylic acid dichloride, diphenylsulphone-4,4-dicarboxylic acid dichloride, benzene-1,3- disulphonic acid dichloride, diphenylmethane-4,4'-dicarboxacid ylic acid dichloride, diphenylsulphide-4,4-dicarboxylic acid 0 dichloride. 4.6-dichloropyrimidine, l-phenyl-3.5-dichloro- 2,4.6-triazine or l-methoxy-3,5-dichloro-2,4,6-triazine. Cyanuryl chloride can also be used.

The dyestuffs of fonnula (2), wherein n=2, may be manu- 1.! An appropriately substituted aniline, which in the 4- position further carries a group which can be converted into an'amino group, is diazotized and coupled to AH. When A contains a free amino group, this group can be acylated.

in the monoazo dyestuff thus obtained, the substituent in the 4-position which has been mentioned is converted into the amino group; the aminoazo dyestuff is then diamtized and coupled to K-H.

When K also contains a free amino group or a group which can be converted into an amino group, this can further be acylated. Disazo or tetrazo dyestufls may be then obtained, as desired.

l.2 An aniline substituted as described under lzl is diazotized and coupled to K-H. Various possibilities exist for the monoazo dyestufl' thus obtained:

l.2.l K contains a free amino group: this can be acylated, the group convertible to an amino group which is also present can then be converted, the compound thus obtained can be diazotized or tetrazotized and coupled with A-H.

1.2.2 K-H is a naphthol: the group which is convertible to an amino group is immediately converted, diazotized and coupled to A--H. If necessary, the radical A can further be acylated.

1.3.] When K-NH is a diazo component: K-NH is diazotized and coupled to an aniline which in the 2- or 3-position contains an SE radical and in the 5- or o-position contains a D- radical. The monoazoamine thus obtained is then diazotized and coupled to AH. When KNH also contains an additional group convertible into an amino group, this group can be converted into the amino group and acylated. Disazo or tetrazo dyestuffs may be obtained, as desired.

1.3.2 When K--NH is a diazo component having a further group convertible into an amino group, KNl-l can first be acylated. Monoacyl or diacyl components are ob tained, as desired. The group or groups convertible into the amino group can then be converted, diazotized or tetrazotized and coupled to an aniline which in the 2- or 3-position contains an SE radical and in the 5- or 6-position contains a D- radical. The monoazoamines or disazoamines thus obtained are diazotized or tetrazotized and coupled to AH.

The dyestuffs of formula (2) wherein rr=l, can also be manufactured according to various known methods.

2.1 An aniline which is suitably substituted and which also carries a group convertible into an amino group in the 4- position, is diazotized and coupled to A-H. When A contains a free amino group, this group can be acylated. The 4-substituent mentioned is then converted into an amino group and the monoazoamine thus obtained is treated with an acylating agent.

2.2 An appropriately substituted 4-nitroaniline is reacted with an acylating agent. Monoanilides or dianilides are obtained, as desired. The nitro group or groups are then reduced, and the product diazotized or tetrazotized and coupled to AH.

Suitable acylating agents are: carboxylic acid anhydrides, for example acetic anhydride, dicarboxylic acid anhydrides, for example glutaric anhydride, carboxylic acid chlorides, for example benzoyl chloride, dicarboxylic acid chlorides, for example terephthaloyl chloride, sulphonic acid chlorides, for example p-toluenesulphonyl chloride, disulphonic acid chlorides, for examplenaphthaIene-l,5-disulphonyl chloride, isocyanates, for example phenylisocyanate, di-isocyanates, for example hexamethylenediisocyanate, ketene and N-heterocyclic compounds, for example l-methoxy-3,5-dichloro-2,4,6- triazine.

The alkylrnercaptoanilines with which the middle components are introduced into the dyestufi's of formula (1) can be manufactured according to two different methods. A lchloro-2-nitro-S-aminobenzene can for example be converted into a l-alkylmercapto-2-nitro-5-aminobenzene by reaction with an alkanethiol and subsequently reduced to the diamine by means of hydrogen and palladium/carbon.

A further method consTsTs of reacting lilfidro-ZritrdS- aminobenzene with sodium disulphide, so that two 2-nitro-5- aminobenzene radicals are linked to one another through an SS bridge, reducing the product with sodium sulphide to the corresponding thiol, converting this product into the corresponding alkylmercapto compound by reaction with a dialkyl sulphate, and then reducing the alkylmercapto compound to the corresponding diamine as previously indicated.

The dyestuffs of formula (1) can also be converted into their heavy metal complexes, by treating them with the corresponding heavy metal compound in an alkaline to weakly acid medium, Thes e heavy metal compounds are advantageously water-soluble and are preferably compohids of metals having ordinal numbers 22 to 29, that is to say compounds of titanium, vanadium, chromium, manganese, nickel or copper. These heavy metal compounds can be derived from inorganic and organic acids, and are for example chlorides, sulphates, nitrates, formates or acetates.

The dyestuffs of formula (1) may be used for various purposes in photographic materials and especially advantageously as image dyestufi's for the silver dyestuff bleaching process. In accordance therewith, valuable photographic materials can be manufactured in the usual manner by known methods, which contain on a layer support at least one layer having a dyestuff offormula (1 In particular, these dyestuffs can be present in a multilayer material which on a layer support contains a selectively redsensitive layer dyed cyan with a dyestuff of formula 1 on top of this a selectively green-sensitive layer dyed with a magenta dyestuff and finally a blue-sensitive layer dyed with a yellow dyestutT. The dyestufis of formula (1) may also be incorporated in an auxiliary layer or especially into a layer adjacent to the light-sensitive layer.

The dyestuffs of formula (1) can also for example, be used for retouching purposes.

In most cases it suffices to add the dyestuffs to be used according to the invention to an aqueous gelatine solution as an aqueous solution or in a solvent which is miscible with Water at normal or slightly elevated temperature with good stirring. Thereafter this mixture is brought together with a gelatine containing silver halide and/or other materials for producing photographic images, cast onto a substrate in the usual manner to give a layer, and dried when necessary.

The dyestuff solution can also be added directly to gelatine containing silver halide and/or other materials for producing photographic images. Thus, for example the dyestufi solution may be added immediately before casting.

Instead of simple stirring, the usual methods of distribution by means of kneading and/or shear forces or ultrasonics can also be employed.

The dyestuff may also be added in solid form or as a paste.

The casting solution can also contain further additives for example curing agents, sequestering agents and wetting agents, as well as sensitizers and stabilizers for the silver halide.

The dyestuffs neither undergo chemical reactions with the light-sensitive materials nor influence their sensitivity to light. The dyestuffs of formula (1) are diffusion-resistant and also form stable, aqueous solutions, they are insensitive to calcium ions and can be bleached white.

On addition to the casting solutions, the dyestuffs neither cause an increase in viscosity nor a significant change in viscosity when the casting mixture is left to stand.

The spectral absorption in gelatine lies in an advantageous region, so that the dyestuffs of formula (1) can be combined with a suitable yellow and magenta dyestufi' to give a triple dyestuff combination which shows grey shades which appear neutral to the eye over the entire density range.

MANUFACTURING INSTRUCTIONS l Alkylmercaptoanilines 1.1 Seventy-one g. of 3-chloro-6-methyl 4-nitroanfline are dissolved in 1,400 ml. of glacial acetic acid at 63 C. Thereafter a total of 150 ml. of acetic anhydride is added in three portions. After a total reaction time of 2% hours at 60 to 70 C. the mixture is cooled to 18 C., and the crystals which have precipitated are filtered, washed with 2 portions of 500 ml. of benzene and dried in vacuo at 70 C. Fifty-five grams of 3-chloro-6-methyl-4-nitroacetanilide of melting point 176 to 177 C. are obtained. A sample recrystallized from benzene melted at 18 1 .4 C.

7.4 g. of 3-chloro-6-methyl-4-nitroacetanilide are dissolved in ml. of ethanol and the solution heated to the boil. A mixture of 4.8 g. of magnesium sulphate, 4.8 g. of Na S.9l-l O and 0.6 g. of sulphur, fused in a test tube, is then added during 5 minutes to the ethanolic solution and the whole is boiled for 3 hours under reflux. After 1% hours a crystalline precipitate forms. At the end of the reaction the mixture is adjusted to pH 1-2 with 10 ml. of 2 N hydrochloric acid and filtered. The residue is washed with 100 ml. of water and dried in vacuo at 60 C. Yield: 5.2 g. of 2,2-dinitro-4,4'-dimethyl-5,5- diacetylaminodiphenyldisulphide of melting point 230 C. (decomposition). 2-Methyl-4nitro-5-methylmercaptoacetanilide 1.8 g. of 2,2 '-dinitro-4,4-dimethyl-5 ,5

diacetylaminodiphenylsulphide are suspended in 50 ml. of water. A solution of 0.7 g. of Na S.9l-l O and 1.5 ml. of 30 percent sodium hydroxide solution and 5 ml. of water is added dropwise thereto. After the mixture has been boiled for 10 minutes under reflux, a clear solution is produced which is filtered hot and l g. of dimethyl sulphate is added dropwise to the filtrate. The mixture is stirred for 30 minutes at 40 C. and stirring is continued overnight at room temperature. The yellow crystals are filtered and washed with 20 ml. of water. The residue is recrystallized from 20 m1. of ethanol. Yield: 0.12 g. of 2-methyl-4-nitro-5-methylmercaptoacetanilide of melting point l55to 158 C. 1.2 An ethanolic solution of 26 g. of potassium methylmercaptide is slowly added dropwise to a solution of 40.5 g. of 2-amino-4-ch1oro-S-nitroanisole in 600 ml. of dimethylformamide at 80 C. The mixture is stirred for 6 hours at 80 C., cooled and poured into 4,000 ml. of cold water, and the product is filtered and washed. AFter drying, 38 g. of 2- methoxy-4-nitro-5-methylmercaptoani1ine of melting point 200 to 201 C. (=89 percent of theory) are obtained.

The following anilines may be manufactured analogously:

Melting point 2-methoxy-4-nitro-5(fl-hydroxyethyl)- mercaptoaniline 170 to 171 C. 2-methy1-4-nitro-5-(fihydroxyethyl)- mercaptoaniline 164 to 165 C. 2-(fl-hydroxyethoxy)-4-nitro-5-(fihydroxyethylj-mercaptoaniline to 151 C. 2-methyl-4-nitro-5-methylmercaptoaniline to 161 C. 3-methylmercapto-4-nitroaniline 145 to 147 C. 3-methylmercapto-4-nitroaniline 179 to 181 C.

1.3 Thirty-two g. of 2-methoxy-4-nitro-S-methylmercaptoaniline together with 300 ml. of 99 percent formic acid are heated for 15 minutes under reflux with stirring. The mixture is then cooled and poured into 1,500 ml. of water. The precipitate is filtered, washed with water and dried in vacuo at 60 C; 35.7 g. of 2-methylmercapto-4-nitro-5-methoxyformamide of melting point 222 to 224 C. are obtained.

12.1 g. of this formanilide are suspended in 300 m1. of methylcellosolve and hydrogenated at room temperature using 1 g. of palladium on active charcoal (10 percent). After completion of the hydrogenation the catalyst is filtered and the solvent is evaporated in vacuo. The oily residue is mixed with 20 ml. of hot n-propanol and 10 ml. of petroleum ether. After cooling, the crystals which separate are filtered and dried; 7.1 g. of 2-methylmercapto-4-formylamino-S-methoxyaniline of melting point 97 to 99 C. are obtained.

.2 Dyestuffs of formula (1) (The spectral data are summarized in tables 1, it AND 111) 2.1 4.6 g. of 2-methoxy-4-nitro-5 toaniline are stirred for 1 hour with 20 ml. of 37 percent hydrochloric acid. Twenty g. of ice are then added and the solution is diazotized with 7 ml. of 4 N sodium nitrate solution. The diazonium solution is slowly poured into a 0.5 percent solution of 14.5 g. of l(p-toluenesulphonylamino)-8- naphthol-3,6-disulphonic acid in 100 ml. of water and 20 g. of ice. The reaction mixture is buffered from pH 2 to 5 with a 7 N potassium acetate solution, and stirred for 3 hours at 0 C. It is then heated to 60 C. and filtered. The residue is dissolved in 300 ml. of water by means of 2 N sodium hydroxide solution methylmercapand then precipitated 600 ml. of a 7 N potassium acetate i solution. After repeated solution and precipitation with 7 N j potassium acetate solution, the product is filtered and the I residue dried in vacuo at 60 C. Yield of nitroazo dyestuffs 16 Fourteen g. of the nitroazo dyestufi' are dissolved in 250 ml. of water at 50 C. A solution of 7.3 g. of Na S.9H O in 10 ml. of water is added thereto and the mixture is stirred for one hour at 50 C. AFter cooling, the reaction mixture is filtered. The azoamine is precipitated with 500 ml. of 7 N potassium acetate solution, filtered and washed with 250 ml. of ethanol. After drying, 7.2 g. of the monoazoamine of the formula CHa- SOzNH OH OCH:

are obtained.

3.3 g. of the monoazoamine of formula (22) are dissolved in 100 ml. of water and mixed with 2 ml. of 4 N sodium nitrite solution. This solution is slowly added dropwise to a solution of 10 ml. of naphthalene sulphonic acid solution (1 liter of this naphthalene sulphonic acid solution contains 1 mol of B- naphthalene sulphonic acid and 1 mol of sulphuric acid) in 50 ml. of ice water. The whole is stirred for one hour at 0 to 4 C 2.5 g. of 2-naphthol-7-sulphonic acid are dissolved in 100 ml. of water and introduced into the above diazo solution at 0 to 2 C. The reaction mixture is adjusted to pH 8 with 250 ml. of pyridine and is then stirred for 12 hours at 0 to 2 C. It is then heated to 50 C. and mixed with 500 ml. of 7 N potassium acetate solution and 700 ml. of methanol. The precipitated dyestuff is filtered, redissolved in water and again precipitated with potassium acetate. After 5-fold precipitation and drying at 80 C., 0.6 g. ofth e dyes tuff ft h e formula 011? s 011? OH s OH;

N=N- N:

HO;S SOJII H300 are obtained. S

The dyestulf of the formula CH -O-S oll m 11 soH.

HO3S SOSH 1130( may be obtained in a similar manner. 2.2 10.5 g. of 2-methoxy-4-nitro-5 toaniline are stirred for IS minutes with 50 hydrochloric acid, mixed with 20 ml. of 4 N sodium nitrite solution at 0 C. and stirred for 1 hour at 0 C. Twenty-four g. of 2-napthol-7-sulphonic acid are dissolved in 400 ml. of water. The above diazo solution is slowly added dropwise to this solution and 150 ml. of a 7 N potassium acetate solution are then added. The reaction mixture is stirred for 12 hours at 0 C. and then heated to 50 C. The resulting precipitate is fil- 1 tered.

The moist precipitate is dissolved in 350 ml. of water at 50 C. and mixed with percent sodium hydroxide solution to l 5 pH 10. Twenty-five g. of Na,S.9H O are then added and the reaction mixture is stirred at 50 C. until reduction is complete. The precipitate formed is filtered, dissolved 3 times in water by heating and precipitated with 20 percent potassium chloride solution. After drying, 6.3 g. of the 20 mpnoazoamine of the formula methylmercapml. of 37 percent 25 HaC are obtained.

2.1 g. of the monoazoamine of formula (23) are diazotized as described in instruction 2.1. The diazo solution thus obtained is added to a solution of 4.2 g. of l-benzoylamino-S- naphthol-4,6-disulphonic acid in 150 ml. of water. The mixture is then treated with 250 ml. of pyridine so that the pH value rises to 7. The mixture is stirred for 12 hours at 0 C., then heated to 50 C. and mixed with 150 ml. of 7 N potassium acetate solution. The dyestufi which has precipitated is filtered. twice dissolved in 200 ml. of hot water/dimethylformamide l:l, and precipitated with 50 ml. of 20 percent ethanolic potassium acetate solution. The product is filtered and washed with 100 ml. of methanol. After drying, 2.3 g. of the dyestuff of formula (III) are obtained.

The dyestuff of formula (Il) may be obtained in a similar manner. 2.3 3.6 g. of Z-methylmercapto-4-fonnylamino-S- methoxyaniline are dissolved in ml. of formic acid. After adding 250 g. of ice, 5 ml. of 4 N sodium nitrate solution are added dropwise and the reaction solution is stirred for a further 30 minutes. 8.5 g. of 2-naphthol-7sulphonic acid are dissolved in 100 ml. of water. The above diazo solution is then added at 0 C. A further 100 g. of ice are then introduced, and then 50 ml. of 7 N potassium acetate solution and 150 ml. of 30 percent sodium hydroxide solution are added. The mixture is stirred for a further 3 hours at 0 to 4 C. and pH 6.5. The

resulting precipitate is filtered, dissolved in 100 ml. of water with 2 N sodium hydroxide solution until the mixture is neutral, precipitated with 10 ml. of 7 N potassium acetate solution and filtered; 6.7 g. of moist azo dyestuff are obtained. This dyestuff is a single substance according to thin layer chromatography.

6.7 g. of this moist azo dyestufi' are suspended in 50 ml. of

37 percent hydrochloric acid and stirred for 15 minutes at 80 to 90 C. AFter cooling, the solid substance is filtered, suspended in 50 ml. of water, and dissolved in 25 percent sodium hydroxide solution to give a neutral solution. The azoamine is precipitated with 20 ml. of 7 N potassium acetate solution. The product is filtered, washed with ethanol and dried at 60 C. in vacuo. Yield: 5.1 g. of monoazoamine of the formula 4 s CH3 HO 0 OH 3 I 17 is j which is a s ingleTu bstance according to thin layer chromatog- (VII) raphy.

2.l g. of the monoazoamine of formula (24) are diazotized Q 1 H s OH H0 as in instruction 2. l. The diazo solution thus obtained is slowly Qadded at 0 to 4 C. to a 50 percent solution of 4.2 g. of 8- N: lbenzoylamino-lnaphthol-3,-disulphonic acid in 150 ml. of

water; 250 ml. of pyridine are then added, whereby the pH HOKS- SOaH 011 0 value rises from 2 to 7. The mixture stirred for a further 12 hours at 0 to 4 0., heated to 50 c. and the dyestuff is n V .9- precipitated by adding 150 ml. of 20 percent ethanolic potassium acetate solution. After filtration, purification and drying, ls obtamed m ofa black powder whlch IS a smgle 2.8 g. of the dyestufiof h f l stance according to thin layer chromatography.

The dyestuffs of formulas (Vlll) to (XVlll) of tables I and Il (VI) may be obtained in a similar manner to that indicated in in- H0 15 structions 2.1 to 2.4. G i 0H S CH3 2.5 3.3 g. of the aminomonoazo dycstufi of formula NzN (25) in the form of the sodium salt are dissolved in 100 ml. of I water and after addition of 4 g. of sodium tetraborate are phosgenated at pH 6.0 to 7.5 until no further starting product H038 S 03H 0 CH3 can be detected by thin layer chromatography.

6 The resulting precipitate is filtered, washed with ethanol and dried; 2.7 g. of the dyestuff of the formula are obtained. EZi 2.4 3.3 g. of the aminomonoazo dyesbuff of the formula Osm-IEH H W a .MM. (2 N= Os Oz-NH OH s 0HJ l HO; ss 03H N=N S OH;

I NH2 H03S S 0311 CHQO N NH CO obtained by diazotiaati mimx ydmethylmercapto-4- V OHEO 2 nitroaniline, coupling to N-benzenesulpho-8-amino-l- '7" 4 naphtol-3,6-disulphonic acid and reduction of the nitro group, :gzg m the form of a dark blue powder with a reddish are dissolved in the form of the sodium salt in 100 ml. of

water, mixed with 5 ml. of naphthalene sulphonic acid solu- The dyesmfiofthe formila Ition (100 ml. of this solution contain one-tenth mol of (XX) naphthalene-Z-sulphonic acid and one-tenth mol of sulphuric 3 OPIIIH 0H acid, that is to say a total of three-tenths equivalent of acid), 40 and diazotized at 5 C. with 1.4 ml. of 4 N sodium nitrate solution.

The mixture is left to react for 1 hour at 5 C. while stirring, Hoas s Dan and the excess sodium nitrite is destroyed by adding the s CH3 requisite amount of sulphamic acid.

The diazo solution is added at 15 C. to a solution of 2.2 g. C0 of 2-naphthol-7-sulphonic acid and 1 g. of sodium tetraborate in ml. of water and 15 ml. of pyridine. The pH value is kept ...a a a at 9.7 during the entire coupling by adding 5 N sodium carmay be obtained in a similar manner. bonate solution. 50 Depending on the way in which they are separated, the After 1 hour the dyestuff which has separated is filtered and y uff of fo m (l) to r i the f m f f acids purified by reprecipitation. or salts, preferably alkali metal salts, for example potassium or T e sqt mgnap iq f ma e V MWEFBL.

TABLE I R NH 11 2 N=N 'N:N I l t; Hots- S 6 H S 0311 Absorption maximum A in run measured in so H ito/DMF Formula No. R] positi on R: R 1:1 Gelatme I 1 3- \S OH; O CH: 612/658 638 CHzOH a." 3- OCH SCH 5 625 ziiiIII "III as 011; CH: 3 624/657 5 2 formula (I) and 3.3 ml. of a silver brfiide emulsion contain-;

TABLE II S OIII Ri-NH OH a N=N- N:

l S 0311 H2 H S OaH Absorption maximum me:- nm measured in SO;H HzO/DMG Formula No. R; position R2 R 1:1 Gelatlne IL. Benzoyl- 8- -SCH3 -OCH3 623/664 604 III .do 4- -SOH OCH; 624/660 601 IV p-Toluenesu1phony1-. 3- -0CH;; SCH; 634 619 I- Benzoyl- 3- OCH SCH 660 598 VII- BenZenesulphonyL. 3- 0CH; SCH 654 618 XIV Benzoyl- 3- SCH CH 616/650 584 XV 4- SCH; CH3 612/646 580 4- OCH; SCH 614/657 616 3- -SCH 0CH 620/658 608 JHzOH xvm do 3- SCH3 -01 577/616 n TABLE III v The processing is then carried out in accordance with the following method R NH OH S CH l a 1. Seven minutes development in a bath WhlCh contains per liter 20 g. of anhydrous sodium sulphite, l g. of 4- methylamino-phenol sulphate, 4 g. of hydroquinone, 10 g. of I d S 03H 0 CH3 anhydrous sodium carbonate and 2 g of potassiumbroml e 2 2. Two minutes stop-fixing in a bath which contains per liter Absorption maximum 200 g. of sodiumthiosulphate, l5 3. of sodium sulphite, 2 5 g.

M. 11111 of crystalline sodium acetate and 13 ml. of glacial acetic acid. measured inijlvo anggne-half minutes washing Formula HzO/DMI 4. Eight minutes colorbleaching in a bath which contains per Gelatin" liter 70 ml. of 37 percent hydrochloric acid, 20 g. of potassium XIX u D Y 600 614 bromide, 50 g. of thiourea and 5 mg. of a color bleaching XX p-Toluenesulphonyl-. CO 548 616 ly ofthe formula The following examples illustrate the invention. (27) NH;

EXAMPLE I 3.3 ml. of a 6 percent gelatine solution, 2.0 ml. of a l per; 7

c e nt aqueous solution of the hardener of the formula? Q T5751; of 1 iiiafiaus solution of the'cyan dyestuff of ing 35 g. of silver per liter are pipetted into a test tube and made up to 10.0 ml. with deionized water. The whole is vigorously mixed and kept for 5 minutes at 40 C. in a water bath.

The casting solution at a temperature of 40 C. is poured onto a glass plate substrate size l3Xl8 cm. After solidification at 10 C., the plate is dried in a drying cabinet with circulating air at 32 C.

A strip cut to 3.5Xl8 cm. is exposed under a step wedge, through a Kodak 2b+49 blue filter with 50 Lux/cm. for 3 seconds.

HOaS

NH: HOgS 5. Two minutes washing. 6. Eight minutes bleaching of residual silver in a bath which contains per liter ml. of 37 percent hydrochloric acid, 40 g. of crystalline copper sulphate and 25 g. of potassium bromide. 7. Two minutes washing. 8. Four minutes fixing as indicated under 2. 9. Ten minutes washing.

A brilliant, light-fast blue-green wedge is obtained which is completely bleached white in the position of the originally greatest silver density.

EXAMPLE 2 The following layers are successively applied to an opaque white acetate film provided with an adhesive layer; 1. Red-sensitive silver bromide emulsion in gelatin, containing the cyan dyestuff of formula (II). 2. Colorless gelatine layer without silver halide. 3. Green-sensitive silver bromide emulsion in gelatine, containing the magenta dyestuff of the formula S 03II l a r m; HO-

0 H H l l 4. Bluesensitive silver bromide emulsion in ing the yellow dyestufiof the formula gelatine, contain- (29) HOQS H lo (3H $M W*N=NQNHO ol L0 OHN-N=N O OH; H30 0 so l Hots The gelatine layers can contain further additives for exam- (30) N ple wetting agents, hardeners and stabilizers for the silver hal-OH3 lide. In other respects the procedure followed is such that the individual layers contain 0.5 g. of the particular dyestuff per Ha square meter of film, and an amount of silver bromide cor- H w responding to l-l.2 g. of silver. *7 V M I x This film is exposed under a colored diapositive with red, is used. A brilliant, very light-fast blue-green wedge is obgreen and blue copying light. The copy is then developed in tained which is completely bleached white in the position of accordance with the following instruction: the originally greatest silver density.

1. Six minutes development in a bath which contains per liter Similar results are Obtained when another dyesluff of tables 50 g. of anhydrous sodium sulphite, 0.2 g. of 1-phenyl-3- I, ll and III is used instead of the dyestuff of fonnula (Ill). pyrazolidone, 6 g. of hydroquinone, 35 g. of anhydrous sodium carbonate, 4 g. of potassium bromide and 0.3 g. of benz- EXAMPLE4 "iazole; A test strip manufactured and exposed in accordance with Five minutes washing; example I using the cyan dyestufi of formula (I) is processed 3. Six minutes fixing in a solution of 200 g. of crystalline sodii accordance i h th foll ing thod; f lhiosulphate and 20 of Potassium metabisulphite in 1 l. five minutes development in a bath which contains per liter Walter; l g. of p-methylaminophenol sulphate, 20 g. of anhydrous mmutes sodium sulphite, 4 g. of hydroquinone, 10 g. of anhydrous 5. Three to twelve minutes color bleaching with a solution Sodium carbonate 2 of potassium bromide and 3 of sodi which contains per liter of water 50 to 80 g. of potassium broum thiocyanate; mide, to 80 g. of thiourea, 35 to 80 g. of 30 percent sulphu- 35 2' two minutes washing; acid and o-ool to (1-01 2- of Color bleaching Catalyst of 3. two minutes treatment in a reversal bath which contains per mulaan; liter 5 g. of potassium bichromate and 5 ml. of 96 percent 6. Ten minutes washing; Sulphuric acid; 7. Five minutes bleaching of residual silver with a solution of 4 Foulminutes hi 60 of crystalline PP Sulphate, 30 8- Of Potassium 4() 5. five minutes treatment in a bath which contains 50 g. of any mide and 15 ml. of 30 percent hydrochloric acid per liter of hydrous di l hi li Water; 6. three minutes washing; Five minutes Washing; 7. four minutes development in a bath which contains per liter 9 Five minutes fixingasindicated under 3; 2 g. of l-phenyl-3-pyrazolidone, 50 g. of anhydrous sodium Five minutes Washing sulphite, 10 g. of hydroquinone, g. of anhydrous sodium A gm-Stable, document-fast Positive Viewing image is carbonate, 2 g. of sodium hexametaphosphate and 20 ml. of a tained. 1 percent aqueous solution of tert.-butylaminoborane;

Similar results are obtained when another dyestuff from one 8. two minutes washing; of tables I, ll or III is used instead of the dyestuif of formula 9. further treatmentas indicated in example 1 under 4 to 9. (m- 50 A brilliant, highly light-fast blue-green wedge running counter to the primary original is obtained. EXAMPLE3 Similar results are obtained when using one of the other 3.3 ml. of a 6 percent gelatine solution, 2.0 ml. of a l perdyestuffs} ofufbleslto cent aqueous solution of the hardener of formula (26), 3.3 ml. 5 5 What cla'med f l of silver bromide emulsion containing 35 g. of silver per liter l F hght'sfinsmve silver hahde emulsion and 1.4 ml. of deionized water are pipetted into a test tube. fnatenal whch contains a support at least one layer of The whole is thoroughly mixed and kept in a water bath at l'3 h. m? 40 C. for 5 minutes.

The casting solution at a temperature of 40 C. is poured on a glass plate substrate size 13X] 8 cm. After solidifying at 10 R C., the plate is dried in a drying cabinet with circulating air at 32 c. D m

A mixture of 3.3 ml. of a 6 percent gelatine solution, 2.0 ml. of a 1 percent aqueous solution of the hardener of formula in which A denotes a hydroxynaphthalene radical which is un- (26), 0.5 ml. of a 1 percent aqueous solution of the cyan substituted or substituted by an amino or hydroxyl group dyestuff of formula (III) and 42 ml, of deionized water i h which is unsubstituted or further substituted, and which conpoured onto the dried layer at 40 C. tains at least one sulfonic acid or sulfonic acid amide group, The material is allowed to solidify and dry as indicated the hydroxyl group being in ortho-position to the azo group, D above. denotes a hydrogen or halogen atom, a lower alkyl, a lower al- A strip cut to 3.5x18 cm. is exposed under a step wedge koxy or a lower hydroxyalkoxy group or an acylamino group, through a Kodak 2b+49 blue filter with 50 Lox/cm, for 10 E denotes a lower alkyl, hydroxyalkyl or carboxyalkyl group, seconds. R denotes an organic radial which is bound to the benzene The procedure described in example 1 is then fQHOWQQ bRL radical through a NH- or N= N bridge, and m denotes which A denotes of the formula an integer having a value of at most 3, the dyestufi containing at least two sulfonic acid groups in the molecule.

2, Photographic material as claimed in claim 1, that contains a dyestuff of the formula E [N=NK] (-1) HOaS 6. Photographic material as claimed in claim 1, that contains a dyestufi of the formula E1 ](n-l) in which E, represents a methyl, ethyl or hydroxyethyl radical, D denotes a hydrogen atom or a methyl or methoxy group, and the radicals D and E,S are in the paraposition to one another and A, G, K, m and n have the significance indicated in claims 1 and 2, the dyestuff containing at least two sulfonic acid groups in the molecule.

7. Photographic material as claimed in claim 1, that conv tains a lbestufi of the formula in which A denotes a hydrogen atom or an amino or hydroxyl group which is unsubstituted or further substituted, p=l or 2, and E, D, G, K, m and n have the significance indicated in claims 1 and 2, the hydroxyl group being in the 1- or 2-position, A, in the 8-position of the napthalene radical and the azo group in the ortho-position to the hydroxyl group, the dyestufi containing at least two sulfonic acid groups in the molecule.

4. Photographic material as claimed in claim 1 that contains a dyestuff of the formula I? [N =NK] (11-1) i A: 0H s H (O a D X1 N/ or 0Xa .XJ in which X, represents a hydrogen atom or a methyl or ethyl group, X represents a hydrogen atom or a methyl, ethyl or cyclohexyl group, a phenyl group which is unsubstituted or. further substituted or an acyl group, the acyl group being derived from an organic monoor poly-carboxylic or -sulfonic acid or from a N-heterocyclic compound containing a hydrocyl group and possessing acid characteristics, X, represents a hydrogen atom or a methyl, ethyl, hydroxyethyl or benzyl group, and E, D, G, K, m, n and p have the significance indicated in claims 1 and 2, the dyestuff containing at least two sulfonic acid groups in the molecule.

5. Photographic material as claimed in claim 1 that contains a dyestuff of the formula E (n-l) in which K is a benzene, naphthalene or pyrazolone radical which is unsubstituted or further substituted, and A, E and D have the significance indicated in claim 1, the dyestufi containing at least two sulfonic acid groups in the molecule.

8. Photographic material as claimed in claim 1 that contains a dyestuffof the formula in which K denotes a naphthol radical which is unsubstituted or substituted by a hydroxyl, alkoxy, hydroxyalkoxy, aralkoxy, amino, monoalkylamino or dialkylamino group in which each alkyl group contains at most five carbon atoms, a cyclohexylamino, phenylamino, carboxylic acid, carboxylic acid amide, sulfonic acid, sulfonic acid amide or acylamino group, the acyl radical being derived from an aliphatic or aromatic monoor poly-carboxylic or -sulfonic acid, and A, D and E have the significance indicated in claim 1, the dyestuff containing at least two sulfonic acid groups in the molecule.

9. Photographic material as claimed in claim 1 that contains a dyestuff of the formula V 7 acid having at most 10 carbon atoms, an aromatic monoor that contains at least one dyestuff of the formula S 03H 25 26 dicarboxylic acid or substituted or unsubstituted N -he tero- Z Z1 cyclic compound containing a hydroxyl group possessing acid characteristics, and A, D, E and m have the significance in- 11 S dicated in claim 1, the dyestuff containing at least two sulfonic acid groups in the molecule. -N=N -N=N- Za l0. Photographic material as claimed in claim 1 that contains a dyestufi'of the formula q H(0 s) SO H 1); HO Y:

E g (song-DH I mm mm g in which Y is a hydrogen atom or a carboxylic acid or carboxrl" ylic acid amide group, and A,, p, E,, D Z, Z and 2;, have the significance indicated in claims 3, 6 and 11, the dyestuff con- D MA 7 4 taining at least two sulfonic acid groups in the molecule. in which 6;, denotes an acyl radical, bound through m acyl i5 13. Photographic material as claimed in claim 1, that congroups to m, Nl-ll groups, of an aliphatic monocarboxylic j fltSgdl/ mfi fgl'm l acid, a substituted or unsubstituted benzene monocarboxylic acid, an aliphatic dicarboxylic acid having at most eight car- A; OH

bon atoms, including carbonic acid, a substituted or unsubs t stituted benzenethiophene, furane or pyridine dicarboxylic N=N NH acid or an aromatic dicarboxylic acid of the formula HOOC-PhM-Ph'COOH in which Ph and Ph' each represents a substituted or unsubstituted phenylene radical and M represents an oxygen or sul- (S O H fur atom or a SO CH CO- or HN-CO- flmjilb a )p-1 s 0 H NH group, m =l or 2, and A, D and E have the significance wh erein denotes an acyl radical bound through m acyl indicated in claim 1, the dyestuff containing at least two sulgroups to m NH groups and, when m =l, a monoacyl fonic acid groups in the molecule. radical of an aliphatic monocarboxylic acid having at most 11. Photographic material as claimed in claim 1 that con five carbon atoms or of a substituted or unsubstituted benzene tains a dyestufi of the formula monocarboxylic acid, and, when m,=2, a diacyl radical of glutaric, furmaric, terephthalic, isophthalic, thiophene-2,5dicarboxylic or pyridine-2,6dicarboxylic acid or a radical of the for- I f OH Y s 4 mula -co or 0c- -c.,i-i,, NH co NH c.,H

CO-, and A p, E,, D and m have the significance in- N=H' dicated in claims 3, 6, l0 and 11, the dyestuff containing at least two sulfonic acid groups in the molecule. (O3 )p1 SOJH Z; I Za D; Z: (s

l4. Photographic material as claimed in claim 1, that contains the dyestufi of the formula a)zn 40 CO-NH OH S-OH2CH2OH 7 OH in which A, denotes a radical of the formula X1 N=N- N=N HO; s s O;H 0cm IIOJS- "rftaagg siimateiafacmtia in claim 1, that a; tains, the dyestuff of the formula in which X, and X haiethe significance indicated in claim 4, and X, denotes a hydrogen atom, a methyl, ethyl or cyclohcxyl group, a phenyl group which may be further substituted or an s 03H acyl group, the acyl group being derived from an aliphatic, I cycloaliphatic or araliphatic monocarboxylic or dicarboxylic CONH x di-carboxylic or sulfonic acid, a heterocyclic monoor di-car- N=N N=N boxylic or a N-heterocyclic compound containing a hydroxyl group and possessing acid characteristics, Z Z and Z each 0311 Con! HO denotes a hydrogen atom or a sulfonic acid or sulfonic acid 7 amide group, r denotes a hydrogen atom a hydroxyl, 16. Photographic material as claimed in claim 1, that conkoxy, hydroxyalkoxy, aralkoxy or alkylamino group, the alkyl tains the dyestuffofthe formula radical in each case containing at most five carbon atoms, or an amino, cyclohexylamino, phenylamino or acylamino group,

the acyl radical having the significance indicated in claim 8, O-oo-rm 0H 5-011; and p, E and D have the significance indicated in claims 3 I and 6, the right-hand side azo group being in the 2- 5- or 8- N=N N=N position of the l-naphthol radical, the dyestuff containing at SOaH least two sulfonic acid groups in the molecule. s 0 H 0 OH; H

12. Photographic material as claimed in claims 8, 11 and 16,

@253? UNITED STATES PATENT OFFICE' CERTIFICATE. OF CORRECTION Patent No- 3, 63 O91 Dated January 11, 1972 lnv n fl HANSROLF LOEFFEL ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 23, claim 2, in the formula change "D to read D Column 22, Claim 1, line 2, delete "of".

Column 25, line 53, after "boxylic" insert Signed and sealed this 14.1311 day of July 1972.

(SEAL) Attest:

EDWARD I LFLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. Photographic material as claimed in claim 1, that contains a dyestuff of the formula
 3. Photographic material as claimed in claim 1, that contains a dyestuff of the formula
 4. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 5. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 6. Photographic material as claimed in claim 1, that contains a dyestuff of the formula
 7. Photographic material as claimed in claim 1, that contains a dyestuff of the formula
 8. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 9. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 10. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 11. Photographic material as claimed in claim 1 that contains a dyestuff of the formula
 12. Photographic material as claimed in claims 8, 11 and 16, that contains at least one dyestuff of the formula
 13. Photographic material as claimed in claim 1, that contains a dyestuff of the formula
 14. Photographic material as claimed in claim 1, that contains the dyestuff of the formula
 15. Photographic material as claimed in claim 1, that contains, the dyestuff of the formula
 16. Photographic material as claimed in claim 1, that contains the dyestuff of the formula 